The present invention relates in general to particles capable of reflecting heat, especially near-infrared radiation, for use in SPD light valves and in SPD light valve suspensions and films and, more specifically, to anisometrically shaped particles of mixed metal oxides such as bismuth manganese oxide pigments useful for such applications.
Light valves have been known for over sixty years for the modulation of light. As used herein, the term xe2x80x9clight valvexe2x80x9d is defined as a cell formed of two walls that are spaced apart by a small distance, at least one wall being transparent, the walls having electrodes thereon usually in the form of transparent conductive coatings. The cell contains a light-modulating element, which may be either a liquid suspension of particles or a plastic film in which droplets of a liquid suspension of particles are distributed.
The liquid suspension (sometimes herein referred to as xe2x80x9ca liquid light valve suspensionxe2x80x9d or simply a xe2x80x9clight valve suspensionxe2x80x9d) comprises small particles suspended in a liquid suspending medium. In the absence of an applied electrical field, the particles in the liquid suspension assume random positions due to Brownian movement, and hence a beam of light passing into the cell is reflected, transmitted or absorbed, depending upon the cell structure, the nature and concentration of the particles and the energy content of the light. The light valve is thus relatively dark in the OFF state. However, when an electric field is applied through the liquid light valve suspension in the light valve, the particles become aligned and for many suspensions most of the light can pass through the cell. The light valve is thus relatively transparent in the ON state. Light valves of the type described herein are also known as xe2x80x9csuspended particle devices,xe2x80x9d or xe2x80x9cSPDsxe2x80x9d.
Light valves have been proposed for use in numerous applications including, e.g., alpha-numeric displays, television displays, windows, sunroofs, sunvisors, filters, mirrors, eyeglasses and the like to control the amount of light passing therethrough or reflected therefrom, as the case may be.
For many applications, as would be well understood in the art, it is preferable for the activatable material, i.e., the light modulating element, to be a plastic film rather than a liquid suspension. For example, in a light valve used as a variable light transmission window, a plastic film, in which droplets of liquid suspension are distributed, is preferable to a liquid suspension alone because hydrostatic pressure effects, e.g., bulging associated with a high column of liquid suspension, can be avoided through use of a film, and the risk of possible leakage can also be avoided. Another advantage of using a plastic film is that, in a plastic film the particles are generally present only within very small droplets and, hence, do not noticeably agglomerate when the film is repeatedly activated with a voltage.
The term, xe2x80x9clight valve filmxe2x80x9d as used herein refers to a film having droplets of a liquid suspension of particles distributed in the film.
U.S. Pat. No. 5,409,734 exemplifies a type of light valve film that is made by phase separation from a homogeneous solution. Light valve films made by cross-linking emulsions are also known. See U.S. Pat. Nos. 5,463,491 and 5,463,492, both of which are assigned to the assignee of the present invention.
For use in set suspensions such as light-polarizing sheets, sometimes called xe2x80x9csheet polarizersxe2x80x9d, which can be cut up and formed into polarized sunglass lenses or used as filters, light-polarizing particles can be dispersed or distributed throughout a sheet of suitable film-forming material, such as cellulose acetate, polyvinyl alcohol or the like. Methods of making set suspensions for use in sheet polarizers are well known in the prior art. It is important to note, however, that the light-polarizing particles used in light-polarizing sheets are immovable, i.e., fixed. See, e.g., U.S. Pat. Nos. 2,178,996 and 2,041,138.
The following is a brief description, for the sake of illustration, of the components of a light valve suspension.
1. Liquid Suspending Media and Stabilizers
A liquid light valve suspension for use in the present invention may be any liquid light valve suspension known in the art and may be formulated according to techniques well known to one skilled in the art. The term xe2x80x9cliquid light valve suspensionxe2x80x9d means, as noted above, a xe2x80x9cliquid suspending mediumxe2x80x9d in which a plurality of small particles are dispersed. The xe2x80x9cliquid suspending mediumxe2x80x9d comprises one or more non-aqueous, electrically resistive liquids in which there is preferably dissolved at least one type of polymeric stabilizer which acts to reduce the tendency of the particles to agglomerate and to keep them dispersed and in suspension.
The liquid light valve suspensions useful in the present invention may include any of the liquid suspending media previously proposed for use in light valves for suspending the particles. Liquid suspending media known in the art which are useful in the invention, include, but are not limited to, the liquid suspending media disclosed in U.S. Pat. Nos. 4,247,175 and 4,407,565. In general, one or both of the liquid suspending medium or the polymeric stabilizer dissolved therein is chosen so as to maintain the suspended particles in gravitational equilibrium.
The polymeric stabilizer, when employed, can be a single type of solid polymer that bonds to the surface of the particles but which also dissolves in the non-aqueous liquid or liquids of the liquid suspending medium. Alternatively, two or more solid polymeric stabilizers may serve as a polymeric stabilizer system. For example, the particles can be coated with a first type of solid polymeric stabilizer such as nitrocellulose which, in effect, provides a plain surface coating for the particles. The coated particles are thereafter re-coated with one or more additional types of solid polymeric stabilizer that bond to or associate with the first type of solid polymeric stabilizer and which also dissolves in the liquid suspending medium to provide dispersion and steric protection for the particles. Liquid polymeric stabilizers may also be used to advantage, especially in SPD light valve films, as described in U.S. Pat. No. 5,463,492.
2. Particles
Inorganic and organic particles may be used in a light valve suspension, and such particles may be either light-absorbing or light-reflecting.
Conventional SPD light valves have generally employed polyhalide particles of colloidal size. The term xe2x80x9ccolloidalxe2x80x9d as used herein means that the particles generally have a largest dimension averaging about 1 micron or less. Preferably, the largest dimension of most of the particles used in a light valve suspension should be less than one-half of the wavelength of blue light, i.e., 2000 Angstroms or less, to keep light scatter extremely low. As used herein, the term xe2x80x9canisometric,xe2x80x9d which refers to particle shape, means that at least one dimension of a particle is larger than another dimension, e.g., the particle length is greater than its width.
A detailed review of prior art polyhalide particles can be found in xe2x80x9cThe Optical Properties and Structure of Polyiodidesxe2x80x9d by D. A. Godina and G. P. Faerman published in The Journal of General Chemistry, U.S.S.R. Vol. 20, pp. 1005-1016 (1950).
Herapathite, for example, is a quinine bisulfate polyiodide, and its formula is given under the heading xe2x80x9cquinine iodosulfatexe2x80x9d as 4C20H24N2O2.3H2SO4.2HI.I4.6H2O in The Merck Index, 10th Ed. (Merck and Co., Inc., Rahway, N.J.). In polyiodide compounds, the iodide anion is thought to form chains and the compounds are strong light polarizers. See U.S. Pat. No. 4,877,313 and Teitelbaum et al. JACS 100 (1978), pp. 3215-3217. The term xe2x80x9cpolyhalidexe2x80x9d is used herein to mean a compound such as a polyiodide, but wherein at least some of the iodide anion may be replaced by another halide anion. More recently, improved polyhalide particles for use in light valves have been proposed in U.S. Pat. Nos. 4,877,313, 5,002,701, 5,093,041 and 5,516,463. These xe2x80x9cpolyhalide particlesxe2x80x9d are formed by reacting organic compounds, usually containing nitrogen, with elemental iodine and a hydrohalide acid or an ammonium halide, alkali metal halide or alkaline earth metal halide.
For the particles to be commercially useful, however, whether or not the light valve suspension is incorporated into a film, it is necessary that the particles have a great chemical and environmental stability. To obtain particles of great environmental stability, in turn, it may be desirable to use non-polyhalide particles in light valve suspensions and films, especially where the stability of the material composing the particles is known to be excellent.
The use of metal particles in light valves was first proposed in U.S. Pat. No. 1,963,496. Many types of metal particles are stable to UV radiation, as well as other environmental stresses. In addition, they are available in a variety of colors, sometimes varying in color as a function of particle size. However, particles comprising two or more metals (mixed metals) and particles comprising mixed metals and oxygen (mixed metal oxides) which, in many cases, are also very stable in response to environmental stresses, have not been previously proposed for use in liquid light valve suspensions, in SPD films, or in light valves.
The present invention is directed, in a first embodiment, to an electro-optical device comprising a cell formed of opposed cell walls, a light modulating unit comprising a suspension containing anisometrically shaped particles of a heat-reflective mixed metal oxide suspended in a liquid suspending medium between the cell walls, and opposed electrodes operatively associated with the cell walls for applying an electrical field across the suspension. The anisometrically shaped heat-reflective particles have an average length in the range between about 1 micron and 50 nanometers, preferably between about 200 nanometers and 50 nanometers, and most preferably between about 75-180 nanometers. In a further embodiment the anisometrically shaped heat-reflective particles have an aspect ratio, i.e., the ratio of length to width, or of largest dimension to smallest dimension, of at least about 3:1, preferably at least about 10:1 and most preferably at least about 20:1.
In one embodiment of the invention the electro-optical device as described above is a light valve, and the suspension is a light valve suspension. Alternatively, in a preferred embodiment, instead of a purely liquid suspension, the anisometric particles of the invention may be suspended in droplets of liquid suspension distributed throughout a polymeric film.
The anisometrically shaped particles may be produced in a variety of physical forms including, but not limited to, fibrils, rods, cylinders, plates, needles, blades, and prisms.
A wide variety of mixed metal oxide pigments are known in the art, which are capable of reflecting infrared radiation and are thus useful in the present invention. Among these are black pigments of chromium iron oxides and of copper chromium oxides. See U.S. Pat. No. 6,221,147 B1 (Sakoske et al), column 5. Preferred particles for use in the invention, however, comprise black pigments of bismuth mangenese oxide. Such particles are also described in detail in U.S. Pat. No. 6,221,147 B1. More preferably the particles comprise Bi2Mn4O10 crystallized in an orthorhombic crystal structure.
An embodiment of the invention involves the incorporation of a plurality of anisometrically shaped particles, having an average length of between about 50-200 nanometers, into a liquid light valve suspension in order to improve the performance of the light valve suspension. The particles may be any anisometric shape as aforesaid, e.g., fibrils, rods, cylinders, plates, needles, blades or prisms and should have an aspect ratio of at least about 3:1, preferably 10:1 and most preferably 20:1.
An additional embodiment of the invention is directed to a method of preparing the anisometrically shaped particles of the invention. The particles may be prepared as a thin film on a substrate, e.g., a film having a thickness of up to 20 nanometers by any appropriate method known in the art, which film can then be cut by any suitable means such as a microtome or a laser into small plates, for example rectangles or squares measuring 200 nanometers or less on a side. The particles cut from the film are then separated from the substrate and from each other by any appropriate method such as but not limited to ultrasonic agitation. If the substrate is soluble, the substrate can be placed in an appropriate solvent, i.e., one capable of dissolving the substrate, and dissolved, leaving undissolved only the cut film mixed metal oxide, which can be ultrasonically or otherwise dispersed, preferably in the presence of a polymeric dispersing agent to prevent particle agglomeration.
In a further embodiment the invention is directed to a film suitable for use as the light modulating unit of an SPD light valve, the film comprising a cross-linked polymer matrix and having droplets of a liquid light valve suspension distributed in the cross-linked polymer matrix. The light valve suspension comprises a plurality of anisometrically shaped mixed metal oxide heat-reflective particles suspended in a liquid suspending medium. The anisometrically shaped particles have an average length of between about 50-200 nanometers. The particles may be produced from any heat-reflective mixed metal oxide such as would be well known among practicioners of ordinary skill in this art including, but not limited to, bismuth manganese oxide pigments, and in a variety of anisometric shapes including, but not limited to fibrils, rods, cylinders, plates, needles, blades and prisms.